Bransfield Strait is a narrow basin separating the South Shetland Islands from the Antarctic Peninsula and is attributed to recent back-arc extension behind the South Shetland volcanic arc. The volcanic islands of Deception and Bridgeman are situated close to the axis of spreading, whereas Penguin Island lies slightly to the north of this axis. The mineralogy, petrology and geochemistry of the lavas of the three volcanoes have been studied in order to provide information on the nature of magmatism associated with the initial stages of back-arc spreading. Deception Island lavas range from olivine basalt to dacite, and all are highly sodic, with high Na/K, K/Rb, Ba/Rb and Zr/Nb ratios and with CeN/YbN = 2. Incompatible elements increase systematically between basalt and rhyodacite, while Sr decreases, suggesting that fractional crystallisation is the dominant process relating lava compositions. The rhyodacites have high concentrations of Zr, Y and the REE and negative Eu anomalies and are compositionally similar to oceanic plagiogranite. Bridgeman Island lavas are mostly basaltic andesites, but the levels of many incompatible elements, including REE, are significantly lower than those of Deception lavas, although CeN/YbN ratios and 87Sr/86Sr ratios (0.7035) are the same. Penguin Island lavas are magnesian, mildly alkaline olivine basalts with a small range of composition that can be accommodated by fractional crystallisation of olivine, clinopyroxene and/or chromite. Penguin lavas have higher 87Sr/86Sr (0.7039) and CeN/ YbN (4) ratios than Deception and Bridgeman lavas. The Rb/Sr ratios of Deception and Penguin basalts (ca. 0.01) are much too low to account for their present 87Sr/86Sr ratios. Modelling suggests that the source regions of the lavas of the three volcanoes share many geochemical features, but there are also some significant differences, which probably reflects the complex nature of the mantle under an active island arc combined with complex melting relationships attending the initial stages of back-arc spreading. Favoured models suggest that Bridgeman lavas represent 10–20% melting and the more primitive Deception lavas 5–10% melting of spinel-peridotite, whereas Penguin lavas represent less then 5% melting of a garnet-peridotite source. The mantle source for Bridgeman lavas seems to have undergone short-term enrichment in K, Rb and Ba, possibly resulting from dewatering of the subducted slab. Hydrous melting conditions may also account for the more siliceous, high-alumina nature and low trace element contents of Bridgeman lavas.